CN106000121A - Solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and preparation method thereof - Google Patents
Solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN106000121A CN106000121A CN201610459976.4A CN201610459976A CN106000121A CN 106000121 A CN106000121 A CN 106000121A CN 201610459976 A CN201610459976 A CN 201610459976A CN 106000121 A CN106000121 A CN 106000121A
- Authority
- CN
- China
- Prior art keywords
- membrane
- preparation
- resistant
- graphene oxide
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 title claims abstract description 17
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 15
- 238000005260 corrosion Methods 0.000 title claims abstract description 10
- 230000007797 corrosion Effects 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 38
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- -1 graphite Alkene Chemical class 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 13
- 238000001471 micro-filtration Methods 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000000108 ultra-filtration Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 17
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000007614 solvation Methods 0.000 description 11
- 239000000975 dye Substances 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- COXVTLYNGOIATD-HVMBLDELSA-N CC1=C(C=CC(=C1)C1=CC(C)=C(C=C1)\N=N\C1=C(O)C2=C(N)C(=CC(=C2C=C1)S(O)(=O)=O)S(O)(=O)=O)\N=N\C1=CC=C2C(=CC(=C(N)C2=C1O)S(O)(=O)=O)S(O)(=O)=O Chemical compound CC1=C(C=CC(=C1)C1=CC(C)=C(C=C1)\N=N\C1=C(O)C2=C(N)C(=CC(=C2C=C1)S(O)(=O)=O)S(O)(=O)=O)\N=N\C1=CC=C2C(=CC(=C(N)C2=C1O)S(O)(=O)=O)S(O)(=O)=O COXVTLYNGOIATD-HVMBLDELSA-N 0.000 description 4
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 210000000433 stratum disjunctum Anatomy 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229960003699 evans blue Drugs 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and a preparation method thereof. The method comprises steps as follows: a mixed liquid of a reduced graphene oxide aqueous solution and ammonia water A flows through a porous supporting membrane, reduced graphene oxide is deposited on the porous supporting membrane, and the composite nanofiltration membrane is obtained; the mixed liquid flows through the porous supporting membrane under the action of pressure. According to the method, the preparation process is simple and easy to implement, the cost is relatively low, the porous supporting membrane used in the method is a microfiltration membrane at the relatively low price, and, however, ultrafiltration membranes in the relatively high price are frequently used in the prior art. A graphene composite nanofiltration membrane organic solvent prepared with the method is high in flux and has the organic dye rejection rate close to 100%. A separation layer of the graphene composite nanofiltration membrane prepared with the method comprises solvated graphene and has very good resistance to various organic solvents and corrosive chemical environments.
Description
Technical field
The present invention relates to a kind of corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant and preparation method thereof, belong to membrane technology neck
Territory.
Background technology
Chemical industry and pharmaceutical industry it is frequently necessary to separating-purifying from organic solution medium go out product or reclaim catalyst.Pass
The purification technique of system, such as evaporation and concentration and distillation, the more and equipment of consuming energy needs to take the biggest space.Cause
This, the expense of separating-purifying process generally to account for whole investment and the 40 of operating cost~70%.And developed in recent years
Organic solvent nanofiltration (OSN) membrane separation technique come is the most simple to operate, efficient, and without phase transformation in separation process,
Can at room temperature carry out.Additionally, OSN membrane separation plant can Highgrade integration, space availability ratio is the highest.Therefore,
The introducing of OSN membrane separation technique is expected to be substantially reduced the cost of chemical separation and purification process.
The critical component of OSN membrane separating process is OSN film.OSN film is usually composite membrane, is made up of two parts:
Fine and close stratum disjunctum and porous support layer.Stratum disjunctum is than relatively thin and compact structure, and aperture is less, determines OSN film and divides
From selectivity and solvent flux.And porous support layer is thicker and aperture is relatively big, mainly provide mechanics for stratum disjunctum
Support.Chemical industry typically requires the substantial amounts of organic solution of process, and this just requires that OSN film has enough in organic media
Stability, and the highest selectivity and solvent flux.Current business-like OSN film mainly has polymeric membrane and pottery
Porcelain film.Macromolecule OSN membrane preparation method is simple, and price is relatively cheap, but organic solvent and soda acid etc. are corroded by it
The toleration of environment is poor.General every kind of macromolecule OSN film be only used for filtering separate specific certain or a few
Organic solvent.Pottery OSN film has good organic solvent tolerance and corrosion resistance, but its technology of preparing requires very
Height, price is expensive.The most important thing is, the macromolecule OSN film of application at present and the organic solvent of pottery OSN film lead to
Measure the least, process during a large amount of organic solution the most oversize, can not meet the demand of industrial quarters.It is thus desirable to provide one
Plant solvent resistant, the high-flux nanofiltration membrane of acid-alkali-corrosive-resisting.
Summary of the invention
It is an object of the invention to provide high-flux nanofiltration membrane of a kind of solvent resistant, acid-alkali-corrosive-resisting and preparation method thereof, solve
NF membrane prepared by existing method of having determined is to organic solvent and caustic chemical environments poor resistance, and solvent flux is too low
Problem.
The preparation method of the corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant provided by the present invention, comprises the steps:
The mixed liquor of the aqueous solution of redox graphene Yu ammonia A is flowed through porous support membrane, described oxygen reduction fossil
Ink alkene deposits on described porous support membrane, i.e. obtains described composite nanometer filtering film.
In above-mentioned preparation method, described mixed liquor flows through described porous support membrane under the effect of the pressure.
In above-mentioned preparation method, described mixed liquor flows through described porous support membrane under the effect of sucking filtration, uses sucking filtration
Bottle can realize.
In above-mentioned preparation method, described graphene oxide can be prepared by Hummers.
In above-mentioned preparation method, described redox graphene is prepared according to the method comprised the steps:
Graphene oxide under conditions of hydrazine hydrate exists through reduction reaction and get final product;
Described reduction reaction and is carried out in water in the basic conditions;
Described graphene oxide is 1:0.71~1.43 with the mass ratio of described hydrazine hydrate.
In above-mentioned preparation method, described alkalescence condition is as follows: by adding in the aqueous solution of described graphene oxide
Ammonia B;
Quality-the volumetric concentration of graphene oxide described in the aqueous solution of described graphene oxide can be 0.1~0.25
Mg/mL, concretely 0.25mg/mL;
The mass fraction of described ammonia B can be 1~25%;
The addition of described ammonia B is: described in every 1mL, the aqueous solution of graphene oxide adds described in 3.92~98 μ L
Ammonia B;Concentration according to ammonia B selects addition, such as, if it adds when the concentration of described ammonia B is 1%
Entering amount is 98 μ L, if the concentration of described ammonia B is 25% its addition is 3.92 μ L.
The temperature of described reduction reaction can be 40~90 DEG C, and the time can be 1~3 hour, as carried out at 40 DEG C 3 hours.
In above-mentioned preparation method, the mass fraction of described ammonia A is 0.1%;
Quality-the volumetric concentration of redox graphene described in the aqueous solution of described redox graphene can be
0.1~0.25mg/mL, such as 0.25mg/mL;
Quality-the volumetric concentration of redox graphene described in described mixed liquor can be 1.5~4.5 μ g/mL, specifically may be used
Be 1.5~2.0 μ g/mL, 1.5 μ g/mL or 2.0 μ g/mL.
In above-mentioned preparation method, described porous support membrane can be high molecule microfilter membrane or anodised aluminium perforated membrane;
The aperture of described porous support membrane is 0.22~0.65 μm.
In above-mentioned preparation method, when described mixed liquor flows completely through described porous support membrane, remove described pressure immediately
Power, can obtain the redox graphene composite nanometer filtering film of solvation, and be stored in water or organic solvent so that answering
The redox graphene layer closed in NF membrane remains Solvation State;Described organic solvent can be methanol, ethanol,
Normal propyl alcohol, isopropanol, n-butyl alcohol, ethylene glycol, glycerol, acetone, oxolane, N,N-dimethylformamide or
N-Methyl pyrrolidone etc..
The corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant that the inventive method prepares falls within the protection model of the present invention
Enclose.
In described composite nanometer filtering film, the load capacity of redox graphene is 33.08~110.27mg/m2。
Redox graphene layer (rGO layer) in composite nanometer filtering film of the present invention keeps Solvation State, is conducive to protecting
Hold its loose structure, thus obtain higher solvent flux.
Composite nanometer filtering film of the present invention is formed in porous support membrane surface stacking by rGO (redox graphene) nanometer sheet,
And making rGO layer remain Solvation State, in composite nanometer filtering film, the load capacity of rGO is 33.08mg/m2~110.27
mg/m2。
Compared with dry rGO film, redox graphene film (S-rGO film) knot of solvation prepared by the present invention
Structure is more loose, thus can obtain higher solvent flux.
Compared with prior art, the present invention has a many advantages:
1, the inventive method preparation process is simple and cost is relatively low, and the porous support membrane that the present invention uses is valency
The micro-filtration membrane that lattice are relatively low, and prior art conventional be the ultrafilter membrane that price is higher.
2, the Graphene composite nanometer filtering film organic solvent flux that the inventive method prepares is high, cuts organic dyestuff
Stay rate close to 100%.
The stratum disjunctum of the Graphene composite nanometer filtering film that 3, the inventive method prepares is made up of solvation Graphene,
Various organic solvents and caustic chemical environments had good toleration.
Accompanying drawing explanation
Fig. 1 is electron scanning micrograph, nylon micro-filtration membrane surface scan electricity during wherein Fig. 1 (a) is embodiment 1
Sub-microphotograph, Fig. 1 (b) is that in embodiment 1, the surface of preparation deposits the nylon micro-filtration membrane table having one layer of S-rGO
Surface scan electron micrograph.
Fig. 2 is UV, visible light (UV-Vis) spectrogram that composite membrane separates, and wherein, Fig. 2 (a) is through embodiment 1
UV, visible light (UV-Vis) spectrogram of azovan blue (EB) methanol solution before and after the S-rGO composite membrane separation of preparation,
Fig. 2 (b) is that methylene blue (MB) methanol before and after the HPEI/S-rGO composite membrane of embodiment 4 preparation separates is molten
The UV-Vis spectrogram of liquid.
Fig. 3 is UV, visible light (UV-Vis) spectrogram that composite membrane separates, wherein, and Fig. 3 (a) and Fig. 3 (b)
It is respectively the UV-Vis spectrogram of AF and BY aqueous solution before and after the S-rGO composite membrane of embodiment 1 preparation separates;
The HPEI/S-rGO composite membrane that Fig. 3 (c) and Fig. 3 (d) is respectively through embodiment 4 preparation separates before and after BF and MB
The UV-Vis spectrogram of aqueous solution.
Fig. 4 is after S-rGO composite membrane prepared by embodiment 2 soaks one day in harsh chemical environments, its methanol flow rate
With the change to EB rejection.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
In following embodiment, composite nanometer filtering film is to water and the flux of various organic solvent, and the rejection to various dyestuffs
Dead-end filtration (dead-end filtration) device of band stirring is tested.Mixing speed 600 rpms during test,
Composite nanometer filtering film pressure at both sides difference is 1~5bar.
Embodiment 1, prepare Graphene composite nanometer filtering film
1, redox graphene is prepared:
1.1 prepare graphene oxide water solution with Hummers, and preparation method is with reference to L.Huang, Y.R.Li, Q.Q.
Zhou,W.J.Yuan,G.Q.Shi,Adv.Mater.,2015,27,3797-3802.
1.2 quality-the volumetric concentrations recording the graphene oxide water solution that step 1.1 prepares are 7.0g/L.
1.3 add water in the graphene oxide water solution that step 1.1 prepares, and are diluted to the oxidation of concentration 0.25g/L
Graphene aqueous solution.
1.4 graphene oxide water solution taking the preparation of 20mL step 1.3, add 78.4 μ L ammonia (mass fractions 25
Wt%), 7.07 μ L hydrazine hydrates (mass fraction 99wt%), now, graphene oxide and the matter of hydrazine hydrate are added
Amount ratio is 1:0.71, pours 30 milliliters of vials after mix homogeneously into.40 DEG C of baking ovens put into by vial after sealing
Middle heated at constant temperature 3 hours, naturally cools to room temperature stand-by in atmosphere after taking-up.
2, the rGO solution (quality-volumetric concentration of rGO is 0.25mg/mL) of 0.15mL step 1.4 preparation is taken,
Being diluted to 25mL with the ammonia of 0.1wt%, now in mixed liquor, the quality-volumetric concentration of rGO is 1.5 μ g/mL, so
After be poured into the bottle,suction being lined with multi-hole micro leaching film, vacuum filtration makes rGO be deposited in micro-filtration membrane.Multi-hole micro leaching film
For diameter 50mm, the nylon micro-filtration membrane of aperture 0.65 μm.
3, when the water in rGO aqueous solution in step 2 just exhausts, stop sucking filtration immediately, i.e. obtain solvation
Redox graphene composite nanometer filtering film.
4, composite nanometer filtering film prepared by step 3 is saved in water so that redox graphene layer remains solvation
State.
Shown in surface Scanning Electron microphotograph such as Fig. 1 (a) of nylon micro-filtration membrane, surface prepared by the present embodiment sinks
Shown in surface Scanning Electron microphotograph such as Fig. 1 (b) of the long-pending nylon micro-filtration membrane having one layer of S-rGO, can by this figure
To find out, it is uniformly deposited on micro-filtration membrane surface through the inventive method rGO.
In S-rGO composite nanometer filtering film prepared by the present embodiment, the load capacity of rGO is 33.08mg/m2。
The pure water flux of S-rGO composite nanometer filtering film prepared by the present embodiment is up to 89.6L/m2H bar, methanol flux is
76.9L/m2h bar。
Fig. 2 (a) is azovan blue (EB) methanol solution before and after the S-rGO composite membrane prepared through the present embodiment separates
UV, visible light (UV-Vis) spectrogram, it can be seen that EB methanol solution is retained by S-rGO composite nanometer filtering film
Rate is up to 100%.
Fig. 3 (a) and Fig. 3 (b) S-rGO composite membrane that respectively prepared by the present embodiment separates before and after's dyestuff acidity product
Red (AF) aqueous solution and UV, visible light (UV-Vis) spectrogram of dyestuff bright orange (BY) aqueous solution, by two figures
It can be seen that in aqueous, S-rGO composite nanometer filtering film bright orange to dyestuff acid fuchsin (AF) and dyestuff (BY)
Rejection be respectively 92.4% and 99.2%.
Embodiment 2, prepare Graphene composite nanometer filtering film
1, redox graphene is prepared:
Prepare according to the method in embodiment 1.
2,0.2mL rGO solution (quality-volumetric concentration of rGO is 0.25mg/mL) is taken, with the ammonia of 0.1wt%
Being diluted to 25mL, now in mixed liquor, the quality-volumetric concentration of rGO is 2.0 μ g/mL, is then poured into and is lined with
The bottle,suction of multi-hole micro leaching film, vacuum filtration makes redox graphene be deposited in micro-filtration membrane.Multi-hole micro leaching film is straight
Footpath 50mm, the nylon micro-filtration membrane of aperture 0.65 μm.
3, when the water in rGO aqueous solution in step 2 just exhausts, stop sucking filtration immediately, i.e. obtain solvation
Redox graphene composite nanometer filtering film.
4, composite nanometer filtering film prepared by step 3 is saved in methanol so that redox graphene layer remains solvent
Change state.
In S-rGO composite nanometer filtering film prepared by the present embodiment, the load capacity of rGO is 44.10mg/m2。
The pure water flux of S-rGO composite nanometer filtering film prepared by the present embodiment is up to 65.5L/m2H bar, methanol flux is
56.2L/m2h bar。
S-rGO composite nanometer filtering film prepared by the present embodiment is up to 100% to the rejection of EB methanol solution.
S-rGO composite nanometer filtering film prepared by the present embodiment at the sulphuric acid of 0.5mol/L or the potassium hydroxide of 0.5mol/L or
After the nitric acid of 0.5mol/L soaks a sky, its methanol flow rate and to the change of EB rejection as shown in Figure 4,
It can be seen that after S-rGO composite membrane soaks one day in harsh chemical environments, remain to keep its nanofiltration performance, have
Well resistance to chemical corrosion.
Embodiment 3, prepare Graphene composite nanometer filtering film
1, redox graphene is prepared:
Prepare according to the method in embodiment 1.
2,0.15mL rGO solution (quality-volumetric concentration of rGO is 0.25mg/mL) is taken, with the ammonia of 0.1wt%
Water is diluted to 25mL, and now in mixed liquor, the quality-volumetric concentration of rGO is 1.5 μ g/mL, is then poured into pad
Having the bottle,suction of multi-hole micro leaching film, vacuum filtration makes redox graphene be deposited in micro-filtration membrane.Multi-hole micro leaching film is
Diameter 47mm, the anodised aluminium perforated membrane of aperture 0.22 μm.
3, when the water in rGO aqueous solution in step 2 just exhausts, stop sucking filtration immediately, i.e. obtain solvation
Redox graphene composite nanometer filtering film.
4, composite nanometer filtering film prepared by step 3 is saved in methanol so that redox graphene layer remains solvent
Change state.
In S-rGO composite nanometer filtering film prepared by the present embodiment, the load capacity of rGO is 33.08mg/m2。
The methanol flux of S-rGO composite nanometer filtering film prepared by the present embodiment is 70.1L/m2h bar。
S-rGO composite nanometer filtering film prepared by the present embodiment is up to 100% to the rejection of EB methanol solution.
Embodiment 4, prepare Graphene composite nanometer filtering film
The redox graphene composite nanometer filtering film of solvation is prepared according to embodiment 1-3.
By in composite nanometer filter film bubble excess of imports branched polyethylene imine (HPEI) aqueous solution (0.1wt%) of above-mentioned preparation, soak
Steep 30 minutes, then clean film with deionized water.The most positively charged HPEI molecule will be adsorbed onto electronegative
On S-rGO film, and composite membrane is made to become positively charged lotus.This composite membrane is referred to as HPEI/S-rGO composite membrane.
Fig. 2 (b) is HPEI/S-rGO composite membrane separation methylene blue (MB) methanol solution prepared through the present embodiment
UV-Vis spectrogram front and back, it can be seen that HPEI/S-rGO composite membrane is to methylene blue (MB) methanol solution
Rejection is up to 90%.
Fig. 3 (c) and Fig. 3 (d) HPEI/S-rGO composite membrane that respectively prepared by the present embodiment separates before and after's dye base
Property pinkish red (BF) aqueous solution and UV, visible light (UV-Vis) spectrogram of dyestuff methylene blue (MB) aqueous solution,
By two figures it can be seen that in aqueous, HPEI/S-rGO composite membrane (BF) and dyestuff pinkish red to dye base
The rejection of methylene blue (MB) is respectively 97.5% and 98.6%.
Claims (9)
1. a preparation method for the corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant, comprises the steps:
The mixed liquor of the aqueous solution of redox graphene Yu ammonia A is flowed through porous support membrane, described oxygen reduction fossil
Ink alkene deposits on described porous support membrane, i.e. obtains described composite nanometer filtering film.
Preparation method the most according to claim 1, it is characterised in that: described mixed liquor is under the effect of the pressure
Flow through described porous support membrane.
Preparation method the most according to claim 2, it is characterised in that: described mixed liquor is under the effect of sucking filtration
Flow through described porous support membrane.
4. according to the preparation method according to any one of claim 1-3, it is characterised in that: described reduction-oxidation graphite
Alkene is prepared according to the method comprised the steps:
Graphene oxide under conditions of hydrazine hydrate exists through reduction reaction and get final product;
Described reduction reaction and is carried out in water in the basic conditions;
Described graphene oxide is 1:0.71~1.43 with the mass ratio of described hydrazine hydrate.
Preparation method the most according to claim 4, it is characterised in that: described alkalescence condition as follows: by
The aqueous solution of described graphene oxide adds ammonia B;
Quality-the volumetric concentration of graphene oxide described in the aqueous solution of described graphene oxide is 0.1~0.25mg/mL;
The mass fraction of described ammonia B is 1~25%;
The addition of described ammonia B is: described in every 1mL, the aqueous solution of graphene oxide adds described in 3.92~98 μ L
Ammonia B;
The temperature of described reduction reaction is 40~90 DEG C, and the time is 1~3 hour.
6. according to the preparation method according to any one of claim 1-5, it is characterised in that: the matter of described ammonia A
Amount mark is 0.1%;
Quality-the volumetric concentration of redox graphene described in the aqueous solution of described redox graphene is
0.1~0.25mg/mL;
Quality-the volumetric concentration of redox graphene described in described mixed liquor is 1.5~4.5 μ g/mL.
7. according to the preparation method according to any one of claim 1-6, it is characterised in that: described porous support membrane is
High molecule microfilter membrane or anodised aluminium perforated membrane.
8. according to the preparation method according to any one of claim 2-7, it is characterised in that: when described mixed liquor is complete
When flowing through described porous support membrane, remove described pressure immediately, and be stored in water or organic solvent.
9. the corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant that prepared by method according to any one of claim 1-8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610459976.4A CN106000121B (en) | 2016-06-22 | 2016-06-22 | A kind of corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610459976.4A CN106000121B (en) | 2016-06-22 | 2016-06-22 | A kind of corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106000121A true CN106000121A (en) | 2016-10-12 |
CN106000121B CN106000121B (en) | 2019-02-05 |
Family
ID=57086395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610459976.4A Expired - Fee Related CN106000121B (en) | 2016-06-22 | 2016-06-22 | A kind of corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106000121B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106621831A (en) * | 2016-12-06 | 2017-05-10 | 中国科学院生态环境研究中心 | Method for performing fast in-situ conversion on microfiltration or ultrafiltration membrane into nanofiltration membrane |
CN106964263A (en) * | 2017-04-27 | 2017-07-21 | 山东金城石墨烯科技有限公司 | A kind of preparation method and application of the graphene NF membrane of solvent resistant resistant |
CN108014657A (en) * | 2016-10-31 | 2018-05-11 | 中国科学院宁波材料技术与工程研究所 | A kind of high-intensity graphene oxide/polyimides mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application |
CN109081430A (en) * | 2018-09-17 | 2018-12-25 | 中车环境科技有限公司 | It can accelerate the preparation method of the reproducibility graphene oxide Modified Membrane of water treatment procedure |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012116286A1 (en) * | 2011-02-25 | 2012-08-30 | Rutgers, The State University Of New Jersey | Scalable multiple-inverse diffusion flame burner for synthesis and processing of carbon-based and other nanostructured materials and films and fuels |
CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
CN105073235A (en) * | 2013-04-12 | 2015-11-18 | 通用电气公司 | Membranes comprising graphene |
CN105251373A (en) * | 2015-09-16 | 2016-01-20 | 清华大学 | Reduced graphene oxide emulsion separating film, and preparation method and application thereof |
-
2016
- 2016-06-22 CN CN201610459976.4A patent/CN106000121B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012116286A1 (en) * | 2011-02-25 | 2012-08-30 | Rutgers, The State University Of New Jersey | Scalable multiple-inverse diffusion flame burner for synthesis and processing of carbon-based and other nanostructured materials and films and fuels |
CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
CN105073235A (en) * | 2013-04-12 | 2015-11-18 | 通用电气公司 | Membranes comprising graphene |
CN105251373A (en) * | 2015-09-16 | 2016-01-20 | 清华大学 | Reduced graphene oxide emulsion separating film, and preparation method and application thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108014657A (en) * | 2016-10-31 | 2018-05-11 | 中国科学院宁波材料技术与工程研究所 | A kind of high-intensity graphene oxide/polyimides mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application |
CN106621831A (en) * | 2016-12-06 | 2017-05-10 | 中国科学院生态环境研究中心 | Method for performing fast in-situ conversion on microfiltration or ultrafiltration membrane into nanofiltration membrane |
CN106621831B (en) * | 2016-12-06 | 2019-05-31 | 中国科学院生态环境研究中心 | A method of it is quickly nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ |
CN106964263A (en) * | 2017-04-27 | 2017-07-21 | 山东金城石墨烯科技有限公司 | A kind of preparation method and application of the graphene NF membrane of solvent resistant resistant |
CN109081430A (en) * | 2018-09-17 | 2018-12-25 | 中车环境科技有限公司 | It can accelerate the preparation method of the reproducibility graphene oxide Modified Membrane of water treatment procedure |
Also Published As
Publication number | Publication date |
---|---|
CN106000121B (en) | 2019-02-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106000121A (en) | Solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and preparation method thereof | |
CN108579475B (en) | Hollow fiber membrane with inner surface subjected to hydrophilic modification, and preparation method and application thereof | |
CN1289177C (en) | Polysulfonamide matrices | |
CN107376673B (en) | Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof | |
CN105169970A (en) | Preparation method for polydopamine-modified polyamide composite forward osmosis membrane | |
CN103394295B (en) | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof | |
CN101249387B (en) | There is the high flux of laminar hole structure, withstand voltage milipore filter and preparation method thereof | |
CN109126480B (en) | Metal organic framework nanosheet modified forward osmosis membrane and preparation method and application thereof | |
US20240238733A1 (en) | Preparation Method for Hollow Fiber Inorganic Membrane | |
CN102974238A (en) | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation | |
CN113769593B (en) | Nanofiltration membrane for extracting lithium from salt lake and preparation method thereof | |
CN109647234B (en) | Preparation method and application of MOF/polymer composite membrane | |
Liu et al. | Boron substituted MFI-type zeolite-coated mesh for oil-water separation | |
JP2005527936A (en) | Method and apparatus for deionizing a coolant for a fuel cell | |
CN107875867B (en) | Transfer-promoting membrane based on amino acid ionic liquid and preparation method and application thereof | |
CN101912741A (en) | Polyamide composite reverse osmosis membrane containing nano materials | |
CN103788364A (en) | Carboxyl-containing polyethersulfone, ultrafiltration membrane, and preparation methods of the carboxyl-containing polyethersulfone and the ultrafiltration membrane | |
CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
CN106964263A (en) | A kind of preparation method and application of the graphene NF membrane of solvent resistant resistant | |
CN109550405B (en) | Preparation method and application of ion selective polymer containing membrane | |
Chen et al. | Highly stable polysulfone solvent resistant nanofiltration membranes with internal cross-linking networks | |
CN109173731A (en) | A kind of method that Freeze Drying Technique prepares metal organic framework@graphene oxide hybridized film | |
CN110257153A (en) | Waste lubricating oil environment protection regeneration method | |
CN116943446A (en) | Composite nanofiltration membrane and preparation method thereof | |
Ravanchi et al. | New advances in membrane technology |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190205 |